Products in acetonitrile

Prohexadione-calcium standard solutions Dissolve 10 mg of prohexadione-calcium in 100mL of water to prepare a lOOmgL" solution. Transfer 100 p.L of this solution into a 30-mL test-tube, evaporate water to dryness under reduced pressure and to methylate prohexadione-calcium according to Section 6.3. Dissolve the product in acetonitrile to prepare the 0.05,0.2,0.4,0.6 and 0.8 mgL acetonitrile solutions. 

In 1978, Saegusa and coworkers discovered that silyl enol ethers can be converted into a,b-unsaturated ketones and aldehydes by Pd" [193]. In the presence of 0.5 equivalents of BQ, substoichiometric Pd(OAc)2 (0.5 equiv) effects nearly quantitative conversion of the substrate into product in acetonitrile (Eq. 51). Attempts to lower the catalyst loading further results in longer reaction times as well as increased yields of saturated carbonyl by-product. 

Interesting solvent effects have also been observed189 [Eq. (9.47)]. Product distribution at secondary sites in water is almost statistical, and ketones are the main products. In acetonitrile, the y position is oxidized with the preferential formation of alcohols. 

A 20 mM solution of the Step 3 product in acetonitrile and A-methyl-A -methoxy-methyl-imidazolium bromide was prepared. The mixture was heated and left to stand at ambient temperature for 30 minutes. An organogel and ionogel formed that were observed using a dark-field optical microscope. The organogel indicated the presence of microcrystals suggesting that they have an associated fibrous structure or that crystals were formed by the slide cover glass the micron-level fibrous structures were not observed in the ionogel. 

Anodic oxidation of primary amines at platinum or carbon electrodes is not of significant preparative interest. The common products in acetonitrile are the aldehydes VI, NH4, nitrogen from the oxidation of ammonia, protonated starting material, and hydrocarbons... 

Note on workup if the final product is soluble in acetonitrile but lacks solubility in hexanes, a solution of the crude product in acetonitrile can be washed several times with hexanes to extract the tin residues.)... 

Carbon dioxide electroreduction can be carried out on modified polypyrrole electrodes [81,82,180]. The active electrodes are obtained by electropolymerizalion of Re(L)(CO)3Cl complex, where L is a pyrrole-substituted ligand of various length. The active species is the immobilized rhenium complex. The main reaction product in acetonitrile is carbon monoxide, and preparative-scale electrolysis gave efficiencies as high as 90%. 

The product distribution ftxim GC analysis of the extracted products in acetonitrile from BaY was approximately 87% benzaldehyde, 4% benzyl alcohol and small amounts of cresol and phenol (3%) and condensation products (2%). Benzyl alcohol and the other products were not readily detected in the FT-IR experiments. 

The oxidation of benzyl alcohol by fra 5 -[Ru (tpy)(0)2(L)] + (L = H2O or MeCN tpy = 1,1 6, 2 -terpyridine) in water or in acetonitrile is first order in alcohol and the ruthenium complex and gives benzaldehyde as the sole oxidation product. In acetonitrile, sequential Ru(VI) Ru(IV) and Ru(IV) Ru(II) steps occur. Ru(II) solvolyses to give [Ru (tpy)(MeCN)3] + and benzaldehyde. On the basis of the 0-labelling results in MeCN, the O atom of the 0x0 group transfers to benzyl alcohol in both steps. In water, Ru(VI) Ru(IV) reduction is followed by rapid dimerization by /U.-OXO formation. Mechanisms are proposed involving prior coordination of the alcohol followed by O insertion into a benzylic C-H bond. ° ... 

The similar procedure was adopted for the synthesis of LCER 2, LCER 3 and LCER 4 as described for the synthesis of LCER 1 with small variations. LCER 2 [4,4 -Di(2,3-epoxypropenyloxy)phe-nyl benzoate] was prepared by oxidizing the diallyl monomer 4,4 -Di(2-propenyloxy)phenyl benzoate (31 g, 0.1 mol) with 3-chlo-roperoxybenzoic acid and recrystallizing the product in acetonitrile/ isopropanol (1 1). Yield 75% (25 g) T 116°C. LCER 3 [p-Phenylene-di[4-(2,3-epoxypropenyloxy)benzoate] was synthesized by oxidizing diallyl monomer p-phenylene-di[4-(2-propenyloxy)benzoate] (13 g, 0.030 mol), obtained pure product after recrystallization from ethylacetate/isopropanol. Yield 68% (8.9 g). The pure product of LCER 4 [4,4 -di[4"-(2,3-epoxypropenyloxy)benzoyloxy]phenyl benzoate] was obtained by oxidizing the diallyl monomer 4,4 -di[4"-(23-epoxypropenyloxy)benzoyloxylphenyl benzoate. "Vleld 66% (7.7 g). 

Figure Bl.16.9. Background-free, pseudo-steady-state CIDNP spectra observed in the photoreaction of triethylamine with different sensitizers ((a), antliraquinone (b), xanthone, CIDNP net effect (c), xanthone, CIDNP multiplet effect, amplitudes multiplied by 1.75 relative to the centre trace) in acetonitrile-d3. The stmctiiral formulae of the most important products bearing polarizations (1, regenerated starting material 2, N,N-diethylvinylamine 3, combination product of amine and sensitizer) are given at the top R denotes the sensitizer moiety. The polarized resonances of these products are assigned in the spectra. Reprinted from [21].

Preparation. In the laboratory, sulfur tetrafluoride is made by combining SCI2 and NaF suspended in acetonitrile at ca 77°C (106). For commercial production, SF is made by direct combination of sulfur with elemental fluorine (107). Commercial appHcations of SF are limited. It is available from Air Products and Chemicals. 

Alkylation. Ben2otrifluoride can also be alkylated, eg, chloromethyl methyl ether—chlorosulfonic acid forms 3-(trifluoromethyl)ben2yl chloride [705-29-3] (303,304), which can also be made from / -xylene by a chlorination—fluorination sequence (305). Exchange cyanation of this product in the presence of phase-transfer catalysts gives 3-(trifluoromethylphenyl)acetonitrile [2338-76-3] (304,305), a key intermediate to the herbicides flurtamone... 

Economic considerations in the 1990s favor recovering butadiene from by-products in the manufacture of ethylene. Butadiene is a by-product in the C4 streams from the cracking process. Depending on the feedstocks used in the production of ethylene, the yield of butadiene varies. Eor use in polymerization, the butadiene must be purified to 994-%. Cmde butadiene is separated from C and C components by distillation. Separation of butadiene from other C constituents is accomplished by salt complexing/solvent extraction. Among the solvents used commercially are acetonitrile, dimethyl acetamide, dimethylform amide, and /V-methylpyrrolidinone (13). Based on the available cmde C streams, the worldwide forecasted production is as follows 1995, 6,712,000 1996, 6,939,000 1997, 7,166,000 and 1998, 7,483,000 metric tons (14). As of January 1996, the 1995 actual total was 6,637,000 t. 

Uranium pentabromide [13775-16-1], UBr, is unstable toward reduction and the pentaiodide is unknown. Two synthetic methods utilized for the production of UBr involve the oxidation of uranium tetrabromide [13470-20-7], UBr, by Br2 or by bromination of uranium turnings with Br2 in acetonitrile. The metastable pentabromide is isostmctural with the pentachloride, being dimeric with edge-sharing octahedra U2Br2Q. 

Oxidopyridazinium betaines isomerize photochemically into pyrimidin-4(3H)-ones (33). Irradiation of 3-oxidopyridazinium betaine or 1-oxidophthalazinium betaine in water affords similarly the corresponding pyridazin-3(2H)-one (35) and phthalazin-l(2H)-one derivative (37). However, photolysis in acetonitrile affords stable diaziridines (34) and (36) which can be converted in the presence of water to the final products (35) and (37) (Scheme 12) (79JCS(P1)1199). 

Table 10 Experimental and Calculated Ni/N Methylation Product Ratios for the Reaction of 3-X,6-Y-Pyridazines with Methyl Iodide in Acetonitrile...

Irradiation of 3,5-disubstituted isoxazoles in alcoholic solvents gave reaction products such as acetals incorporating the reaction solvent. The use of triethylamine in acetonitrile media produced ketene-aminals by reductive ring cleavage. The reductive ring cleavage product was also obtained by irradiation of the isoxazole in alcohol in the presence of copper(II) salts (Scheme 3) (76JCS(P1)783). 

The major product obtained from the reaction of TeCU with (McsSijsN is determined by the stoichiometry. When approximately equimolar amounts of the two reagents in THF are used the dimeric cluster TceNs (stabilized by coordination to four TeCU molecules) is obtained in high yields (Section 5.2.8). When the same reaction is carried out in acetonitrile with a molar ratio of 2 1, followed by treatment of the product with AsFs in SO2, [Tc4N2Cl8][AsF6]2 is obtained Section The dication [Tc4N2Cl8] in this salt is the dimer of the hypothetical tellurium(IV) imide [Cl3Te-N=TeCl]. ... 

When N alkylation is not possible forsterie reasons, C alkylation appears to occur directly (55). Solvents of high dielectric also favor C alkylation 27,29). Thus l-N-pyrrolidino-2-methyl-l-propene (22) with allyl bromide in ether gave only 20 % of C-alkylated product, while in acetonitrile over 50% of this product is obtained. 

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